CN105016733A - Graphene composite B4C superhard material preparation method - Google Patents
Graphene composite B4C superhard material preparation method Download PDFInfo
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- CN105016733A CN105016733A CN201510439690.5A CN201510439690A CN105016733A CN 105016733 A CN105016733 A CN 105016733A CN 201510439690 A CN201510439690 A CN 201510439690A CN 105016733 A CN105016733 A CN 105016733A
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- superhard material
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Abstract
A graphene composite B4C superhard material preparation method is characterized by comprising the following steps: graphene oxide with the sheet diameter greater than 1mum and the layer number not more than five is mixed with B4C powder with the particle size not more than 3mum, the graphene oxide volume fraction is 0.3% -5%, water with the mass of 20-40 times of the mass of the B4C are added for ultrasonic treatment for 10-30min to obtain a graphene oxide / B4C mixture liquid, the graphene oxide / B4C mixture liquid is stirred for 2h more for more uniform mixing, and finally the graphene oxide / B4C mixture liquid is stirred and dried at a drying temperature below 100 DEG C at atmospheric pressure to obtain mixed powder; the mixed powder is pre-pressed into an initial blank in a molding apparatus; the initial blank is put into a high temperature and high pressure apparatus for high pressure sintering to obtain a graphene composite B4C superhard material, wherein the sintering temperature 1300-1600 DEG C, the sintering pressure is greater than 3GPa, and the sintering time is greater than 10min. The superhard material is harder than 19GPa, the fracture toughness reaches 8.76MPa. m1 / 2, and the fracture toughness of the graphene composite B4C superhard material is improved by more than 1 times compared with that of a pure B4C material.
Description
Technical field
The present invention relates to a kind of preparation method of superhard material, be specially and utilize high-temperature high-pressure apparatus sintering to prepare Graphene compound B
4the method of C superhard material.
Background technology
Along with the needs of industrial development and the continuous breakthrough of Materials science and innovation, various high strength, high rigidity, anticorrosive and resistant to elevated temperatures type material are arisen at the historic moment.As the important component part of this family, superhard material demonstrates wide application prospect in fields such as machinery, electronics, computer, space flight and aviation.As the important member in superhard material family, B
4c is owing to having high strength, high rigidity, a series of excellent properties such as high temperature resistant, wear-resistant, corrosion-resistant and receiving much concern, and its hardness is only second to diamond and cubic boron nitride.But the fracture toughness property of stupalith is general lower, B
4c is no exception, and its toughness is 3.2MPam
1/2, an order of magnitude at least lower than the toughness of metallic substance.This makes its poor processability, very easily produces tiny crack and damage, constrains it to a great extent and apply.Therefore improve the fragility of carbide superhard material, increase its intensity, improve its reliability in actual applications and become the key that can this material be widely used.
Research shows, adding toughner is improve B
4the effective way of C superhard material mechanical characteristic.Such as, B
4c-(40-60vol%) TiB
2the fracture toughness of matrix material is 4.5MPam
1/2(S.G.Huang, K.Vanmeensel, O.I.A Malek, O.Van.der Biest, J.Vleugels, Microstructure and mechanical properties of pulsed electric current sinteredB
4c-TiB
2composites, Mater.Sci.Eng., A 528,1302,2011); B
4c-(40vol%) Al
2o
3(about 1wt%SiC additive) (A.K.Swarnakar, S.G.Huang, O.Van der Biest, J.Vleugels, Ultrafine Al
2o
3-B
4c composites consolidated by pulsed electriccurrent sintering, J.Alloys Compd., 499,200,2010) or B
4c-(4wt%) CeO
2the fracture toughness of matrix material reaches 6.0MPam
1/2(Sh-Ch.Sun, T.Sakamoto, K.Nakai, H.Kurushita, S.Kobayashi, J-Y.Xu, H.Cao, B.Gao, X.Bian, W-Y.Wu, G-F.Tu, S.Matsuda, Microstructures and mechanical properties in B
4c-CeO
2ceramics, J.Nucl.Mater., 417,663,2011).
Graphene is the material that current mankind's known strength is the highest, also harder than diamond, and the best in the world iron and steel of strength ratio is high 100 times, and Young's modulus is about 1000GPa, and elastic stretching is about 20%, has good snappiness.Therefore, compared with other toughening materials, the specific surface area that Graphene is huge and good mechanical property make it may become more outstanding ceramic toughening agent.Such as, the method that the people such as Luke S.Walker in 2011 adopt discharge plasma to sinter has synthesized Graphene/silicon nitride pyroceramic, and the fracture toughness of this matrix material improves about 135% (by 2.8MPam after tested
1/2bring up to 6.6MPam
1/2) (L.S.Walker, V.R.Marotto, M.A.Rafiee, N.Koratkar, E.L.Corral, Toughening in graphene ceramic composites, ACSNano, 5,3182,2011).This composite ceramics forms with discharge plasma sintering technology high temperature (1650 DEG C) sintering under intimate normal pressure (35MPa) state.But for B
4c, the preparation condition of this superhard material requires harsh, and normal pressure-sintered temperature is greater than 2000 DEG C, and success carries out Graphene compound and prepares the Graphene compound B that fracture toughness is significantly improved at such high temperatures
4c material is a great problem always.Condition of high voltage (GPa) can make sintering temperature significantly decline, may ensure Graphene can stable existence in matrix material not destroy by high temperature, simultaneously high pressure is beneficial to and obtains high fine and close block materials, so high-pressure sinter is expected to successfully composite graphite alkene and prepares the Graphene compound B that fracture toughness significantly improves
4c material.
Summary of the invention
Object of the present invention is mainly that the method utilizing High Temperature High Pressure to sinter prepares Graphene compound B
4c superhard material.
The concrete technical scheme that the present invention adopts is:
A kind of Graphene compound B
4the preparation method of C superhard material, is characterized in that the step of the method successively:
(1) sheet footpath is greater than 1 μm, the number of plies is no more than the B that the graphene oxide of 5 layers and particle diameter are not more than 3 μm
4c powder mixes, and wherein the volume fraction of graphene oxide is 0.3%-5%, then adds B
4the 20-40 water doubly of C quality, obtains graphene oxide/B after ultrasonic 10-30min
4c mixed solution, then stirs more than 2h, makes this mixed solution more even, is finally dried with the bake out temperature atmospheric agitation lower than 100 DEG C by this mixed solution and obtains mixed powder;
(2) mixed powder is pressed in molding device just base in advance;
(3) first base is put into high-temperature high-pressure apparatus and carry out high-pressure sinter, wherein sintering temperature 1300-1600 DEG C, sintering pressure is greater than 3GPa, and sintering time is greater than 10min, obtains Graphene compound B
4c superhard material.
Further scheme is molding device can be tabletting machine or other molding device.
Further scheme is high-temperature high-pressure apparatus can be six-plane piercer or other high-temperature high-pressure apparatus.
In the present invention, ultrasonic object is full and uniform in order to realize mixing; Described stirring can adopt magnetic stirrer; Sintering pressure is greater than 3GPa, the time, to be greater than 10min be all to can fully sinter; In High Temperature High Pressure sintering process, graphene oxide has been reduced into Graphene.
Advantage of the present invention and effect are: utilize High Temperature High Pressure sintering process successfully to prepare Graphene compound B first
4c superhard material, and achieve B by the method for composite graphite alkene
4c superhard material toughness reinforcing.The Graphene compound B that the method obtains
4the fracture toughness of C superhard material is than pure B
4c improves more than 1 times, has certain prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the Graphene compound B of gained of the present invention
4the SEM figure of C superhard material.
Fig. 2 is the Graphene compound B of gained of the present invention
4the HRTEM figure of C superhard material.
Fig. 3 is the Graphene compound B of gained of the present invention
4c superhard material and pure B
4the Raman spectrum comparison diagram of C material.
Fig. 4 is the Graphene compound B of gained of the present invention
4c superhard material and pure B
4the hardness of C superhard material, fracture toughness comparison diagram.
Embodiment
Below by specific embodiment to Graphene compound B of the present invention
4the preparation of C superhard material further illustrates.
Embodiment 1
(1) by 0.3g B
4c and volume fraction be 0.3% graphene oxide mix, add 20g water, ultrasonic 20min obtains graphene oxide/B
4c mixed solution; Then use magnetic stirrer 3h, make it mix more even; Finally by the graphene oxide/B of gained
4c mixed solution obtains mixed powder at 90 DEG C of stirring and dryings.
(2) mixed powder being pressed in tabletting machine diameter is 8mm, the high right cylinder for 4mm just base.
(3) first base is put into six-plane piercer, 1400 DEG C, sinter 20min under 4.5GPa, obtain Graphene compound B
4c superhard material.
Embodiment 2
(1) by 0.5g B
4c and volume fraction be 0.6% graphene oxide mix, add 30g water, ultrasonic 20min obtains graphene oxide/B
4c mixed solution, then uses magnetic stirrer 3h, makes it mix more even, finally by the graphene oxide/B of gained
4c mixed solution obtains mixed powder at 80 DEG C of stirring and dryings.
(2) mixed powder being pressed in tabletting machine diameter is 8mm, the high right cylinder for 6mm just base.
(3) first base is put into six-plane piercer, 1350 DEG C, sinter 30min under 4.5GPa, obtain Graphene compound B
4c superhard material.
Embodiment 3
(1) by 1g B
4c and volume fraction be 0.9% graphene oxide mix, add 25g water, ultrasonic 25min obtains graphene oxide/B
4c mixed solution, then uses magnetic stirrer 5h, makes it mix more even, finally by the graphene oxide/B of gained
4c mixed solution obtains mixed powder at 80 DEG C of stirring and dryings.
(2) mixed powder being pressed in tabletting machine diameter is 12mm, the high right cylinder for 5mm just base.
(3) first base is put into six-plane piercer, 1300 DEG C, sinter 25min under 5GPa, obtain Graphene compound B
4c superhard material.
Embodiment 4
(1) by 1g B
4c and volume fraction be 1.8% graphene oxide mix, add 30g water, ultrasonic 15min obtains graphene oxide/B
4c mixed solution, then uses magnetic stirrer 6h, makes it mix more even, finally by the graphene oxide/B of gained
4c mixed solution obtains mixed powder at 90 DEG C of stirring and dryings.
(2) mixed powder being pressed in tabletting machine diameter is 10mm, the high right cylinder for 7mm just base.
(3) first base is put into six-plane piercer, 1400 DEG C, sinter 10min under 4GPa, obtain Graphene compound B
4c superhard material.
Embodiment 5
(1) by 2g B
4c and volume fraction be 3% graphene oxide mix, add 35g water, ultrasonic 30min obtains graphene oxide/B
4c mixed solution, then uses magnetic stirrer 4h, makes it mix more even, finally by the graphene oxide/B of gained
4c mixed solution obtains mixed powder at 80 DEG C of stirring and dryings.
(2) mixed powder being pressed in tabletting machine diameter is 16mm, the high right cylinder for 6mm just base.
(3) first base is put into six-plane piercer, 1500 DEG C, sinter 10min under 3GPa, obtain Graphene compound B
4c superhard material.
Embodiment 6
(1) by 0.5g B
4c and volume fraction be 3% graphene oxide mix, add 30g water, ultrasonic 20min obtains graphene oxide/B
4c mixed solution, then uses magnetic stirrer 3h, makes it mix more even, finally by the graphene oxide/B of gained
4c mixed solution obtains mixed powder at 80 DEG C of stirring and dryings.
(2) mixed powder being pressed in tabletting machine diameter is 8mm, the high right cylinder for 6mm just base.
(3) first base is put into six-plane piercer, 1300 DEG C, sinter 30min under 5GPa, obtain Graphene compound B
4c superhard material.
Here is Graphene compound B
4the structure of C superhard material, morphology characterization:
1. morphology analysis
Fig. 1 is Graphene compound B
4the SEM figure of C superhard material, graphene uniform is dispersed in B as seen from the figure
4in C particle.Wherein part Graphene is present in B
4between C particle, part Graphene is wrapped in B
4c particle surface.
Fig. 2 is Graphene compound B
4the HRTEM figure of C superhard material, Graphene is in B as seen from the figure
4between C crystal boundary.
2. structural analysis
Fig. 3 is Graphene compound B
4c superhard material and pure B
4the Raman spectrum comparison diagram of C material.Compared to simple substance B
4c, Graphene compound B
4having there is obvious Graphene peak in C superhard material, proves that Graphene successfully adds B to
4in C matrix.
Here is Graphene compound B
4the performance test such as hardness, fracture toughness of C superhard material:
Fig. 4 is the increase with Graphene volume fraction, Graphene compound B
4the hardness of C superhard material and fracture toughness changing trend diagram.The visible raising along with Graphene volume fraction, composite hardness declines to some extent, but still higher than 19GPa, and fracture toughness is from 3.79MPam
1/2bring up to 8.76MPam
1/2, improve more than 1 times.Illustrate that this method of Graphene compound effectively can improve B
4the fracture toughness of C superhard material.
Claims (3)
1. a Graphene compound B
4the preparation method of C superhard material, is characterized in that the step of the method successively:
(1) sheet footpath is greater than 1 μm, the number of plies is no more than the B that the graphene oxide of 5 layers and particle diameter are not more than 3 μm
4c powder mixes, and wherein the volume fraction of graphene oxide is 0.3%-5%, then adds B
4the 20-40 water doubly of C quality, obtains graphene oxide/B after ultrasonic 10-30min
4c mixed solution, then stirs more than 2h, makes this mixed solution more even, is finally dried with the bake out temperature atmospheric agitation lower than 100 DEG C by this mixed solution and obtains mixed powder;
(2) mixed powder is pressed in molding device just base in advance;
(3) first base is put into high-temperature high-pressure apparatus and carry out high-pressure sinter, wherein sintering temperature 1300-1600 DEG C, sintering pressure is greater than 3GPa, and sintering time is greater than 10min, obtains Graphene compound B
4c superhard material.
2. Graphene compound B according to claim 1
4the preparation method of C superhard material, is characterized in that molding device is tabletting machine.
3. Graphene compound B according to claim 1
4the preparation method of C superhard material, is characterized in that high-temperature high-pressure apparatus is six-plane piercer.
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Cited By (10)
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| CN107245713A (en) * | 2017-05-25 | 2017-10-13 | 中北大学 | Laser melting coating repairs spheroidal graphite roll surface alloy powder |
| CN107840661A (en) * | 2017-10-27 | 2018-03-27 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of boron carbide ceramics piece |
| CN108383527A (en) * | 2018-03-21 | 2018-08-10 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of graphene/carbon boron ceramic composite |
| CN108516832A (en) * | 2018-04-12 | 2018-09-11 | 南京理工大学 | A kind of the boron carbide ceramics material and its preparation process of graphene toughening |
| CN108530082A (en) * | 2018-06-20 | 2018-09-14 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of graphene enhancing boron carbide ceramics material |
| CN111116203A (en) * | 2020-02-28 | 2020-05-08 | 中国工程物理研究院流体物理研究所 | Preparation method of high-density nano boron carbide ceramic material |
| CN111470515A (en) * | 2020-05-12 | 2020-07-31 | 江苏冠军科技集团股份有限公司 | Graphene-boron carbon nanosheet and application thereof, graphene-boron carbon nanosheet doped anticorrosive coating and preparation method thereof |
| CN111499385A (en) * | 2020-03-19 | 2020-08-07 | 武汉理工大学 | Boron carbide-graphene micro-laminated composite material and preparation method thereof |
| US10981836B2 (en) | 2018-05-15 | 2021-04-20 | University Of South Carolina | Laser induced graphitization of boron carbide in air |
| CN112723889A (en) * | 2021-02-05 | 2021-04-30 | 武汉理工大学 | High-strength and high-toughness boron carbide-titanium boride-graphene composite ceramic and preparation method thereof |
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| CN107245713B (en) * | 2017-05-25 | 2019-02-26 | 中北大学 | Laser melting coating repairs spheroidal graphite roll surface alloy powder |
| CN107245713A (en) * | 2017-05-25 | 2017-10-13 | 中北大学 | Laser melting coating repairs spheroidal graphite roll surface alloy powder |
| CN107840661A (en) * | 2017-10-27 | 2018-03-27 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of boron carbide ceramics piece |
| CN108383527A (en) * | 2018-03-21 | 2018-08-10 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of graphene/carbon boron ceramic composite |
| CN108383527B (en) * | 2018-03-21 | 2022-02-22 | 浙江立泰复合材料股份有限公司 | Preparation method of graphene/boron carbide ceramic composite material |
| CN108516832A (en) * | 2018-04-12 | 2018-09-11 | 南京理工大学 | A kind of the boron carbide ceramics material and its preparation process of graphene toughening |
| US10981836B2 (en) | 2018-05-15 | 2021-04-20 | University Of South Carolina | Laser induced graphitization of boron carbide in air |
| CN108530082A (en) * | 2018-06-20 | 2018-09-14 | 浙江立泰复合材料股份有限公司 | A kind of preparation method of graphene enhancing boron carbide ceramics material |
| CN111116203A (en) * | 2020-02-28 | 2020-05-08 | 中国工程物理研究院流体物理研究所 | Preparation method of high-density nano boron carbide ceramic material |
| CN111116203B (en) * | 2020-02-28 | 2022-01-21 | 中国工程物理研究院流体物理研究所 | Preparation method of high-density nano boron carbide ceramic material |
| CN111499385A (en) * | 2020-03-19 | 2020-08-07 | 武汉理工大学 | Boron carbide-graphene micro-laminated composite material and preparation method thereof |
| CN111499385B (en) * | 2020-03-19 | 2021-03-16 | 武汉理工大学 | Boron carbide-graphene micro-laminated composite material and preparation method thereof |
| CN111470515B (en) * | 2020-05-12 | 2021-09-10 | 江苏冠军科技集团股份有限公司 | Graphene-boron carbon nanosheet and application thereof, graphene-boron carbon nanosheet doped anticorrosive coating and preparation method thereof |
| CN111470515A (en) * | 2020-05-12 | 2020-07-31 | 江苏冠军科技集团股份有限公司 | Graphene-boron carbon nanosheet and application thereof, graphene-boron carbon nanosheet doped anticorrosive coating and preparation method thereof |
| CN112723889A (en) * | 2021-02-05 | 2021-04-30 | 武汉理工大学 | High-strength and high-toughness boron carbide-titanium boride-graphene composite ceramic and preparation method thereof |
| CN112723889B (en) * | 2021-02-05 | 2022-09-13 | 武汉理工大学 | High-strength and high-toughness boron carbide-titanium boride-graphene composite ceramic and preparation method thereof |
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Application publication date: 20151104 |